Tetrakisazo dyestuffs



United States Patent Q i v 2,7 97 ,214 TETRAKISAZO DYESTUFFS WernerrBssard,-Riehen, near Basehswitzerland', assignor to-"L Rs Geigy A. Gi, Basel,- S'witzerland, a Swiss firm No Drawing; ApplicationFbruary 15, 1954, Serial No. 410,410

Glairns priority, application-Switzerland March '6, 1953 '7 Claims. or. 260-153 The present invention concerns aprocessifor the product-ionjf ofmetallisable tetrakisazo dyestuifs,.tlie cop- PBredcellulose dyeingsof which have very. goodfastness properties. i I

It has been found that valuable metallisable tetrakisazo dyestuffs are obtained if 2 mols oftlie same or" different diazonium compounds of amino mo'noazo dyestufis of the general formula:

Hm GM 1 HOQNH-C 0 wherein are coupled with 1 mol of a compound of the general formula:

wherein B represents a bridging member which links the nitrogen atoms of the phenyl amino groups withthe-aid of acid functional groups of carbon.

Particularly favourable amino monoazo dyestuffs usable according to the present invention correspond to the general formula:

Y o uni-o 0 0H no 0 c N: -NH:

2,797,214 Patented June 25, 1957 in particular the radical of cyanuric acid, .the radical of aliphaticor aromatic dicarboxylic acids such'as, e. g. oxalic-acid,- succinic acid; pimelic acid, adipic acid, sebacic'acid, fumaric acid, dimethyl ether dicarboxylicacid, thiodi'glycolic acid, isoor terephthalic 'acid. It can also be withadvantage the dicarbonic acid half ester radical of aliphatic diols,'.e. g. thatofethylene glycol, of 1.2- or 1.3-dihydroxypropane, of 1.4-or 2.3-dihydroxybutane, of fl.B:'-dihydroxydiethyl ether, of B.[3'-dihydroxydiethyl sulphide, of 'w.w-dihydroxy-triethylene diether.

' Coupling components usable accordingv to the present invention are obtained by reacting 2-(4-aminophenylamino)-5-hydroxynaphthalene-7-su1phonic acid, advantageouslyj. the form'o'f the aqueous solution of its alkali'ime'tal. salts, with the acid halides co'rresponding'to th'e bridgingmember B untilthe primary amino group disappfears,.i. e. .for example with .phosgene, thiophosgene;- cyanuric -acid.chloride-in whichreaction it is of advantage to replace the third halogen atom thereof by ammonia, primary or secondary amineswith dicarboxylic acidchlorides or bromides of the dicarboxylic acids mentioned above or with the-"dichlo'rocarbonic acid esters of the di'ols listed above.

The amino monoazo dyestuffs usable. according to this invention are diazotised according to the usual methods inca mineral acid aqueous solution or suspension with sodium nitrite and the coupling with the derivatives of 2'-'-('4" aminophenylamino) 5 hydroxynaphthalene 7- sulphonic acid is performed in an alkaline'mediurn, ad- '30" vantageously inthe presence'of'tert'iary nitrogen bases such-as pyridine bases or ethanolamines which accelerate the coupling.

In the form of their alkali metal salts, the metallisable tetrakisazo dyestuffs according to the present invention are dark powderswhich dissolve in'water with a more or less pure blue colour according to the composition, and'theydissolve in concentrated sulphuric acid with a blue-black to black-green colour. They dye cellulose fibres from a bath containing Glaubers salts in blue to green-blue shades Which-are fixed fast to Wet and light by coppering.

The dyestuffs according to the present invention can be copperedin substance, but-it is more advantageous to copper on the fibre. The direct cellulose dyeings can be coppered in the dyebath or in a fresh bath in a neutral to weakly acid medium with the usual copper salts, such as for example, copper acetate or copper sulphate. If desired copper compounds which are stable to alkalies can be used such as those obtained on the reaction of copper sulphate with sodium tartrate in a soda alkaline bath. The coppering can'also be performed at the same time as the dyeings are treated with agents to improve the wet fastness and fastness to creasing, e. g. together with dimethylol urea or with trimethylol melamine. Also resins containing copper'can be used such as are obtained by treating formaldehyde condensation products of biguanide compounds with copper salts.

The following examples illustrate the invention without limiting it in any way. Parts are given as parts by weight and the temperatures are in'degrees centigrade.

Example 1 28.6 parts of 5-(3-methyl-4-amino'benzoylamino)-2- hydroxybenzene-l-carboxylic acid and 4 parts of sodium blue shades which, on treating with copper salts, only hydroxide are dissolved in 400 parts of water, mixed with 6.9 parts of sodium nitrite and the whole is poured at 20 on to 40 parts of concentrated hydrochloric acid. The yellow-brown suspension of the diazonium compound which has been neutralised with 4.5 .parts of 5 sodium carbonate is coupled with 29.7 parts of l-amino- 2-naphthyl glycolic acid-6-sulph-onic acid in the presence hydroxynaphthaleneJ-sulphonic acid, then similar dyestutr's with similar properties are obtained.

Example 2 27.2 parts of 5-(4'-aminobenzoylamino)-2-hydroxybenzene-l-carboxylic acid are diaz-otised in the usual way of 20 parts of sodium acetate. The reaction is kept and coupled in a weakly acid solution with 21.7 parts of weakly acetic acid by the dropwise addition of 5.3 parts l-amino-Z-naphthyl glycolic acid in 600 parts of water. of sodium carbonate in 50 parts of water. After some 10 The monoazo dyestuif suspension formed is mixed with time, 500 parts of sodium chloride and 100 parts of mm 500 parts of sodium chloride and 100 parts of concencentrated hydrochloric acid are added and then 9 parts trated hydrochloric acid and a solution of 9 parts of of sodium nitrite in 27 parts of water are slowly poured sodium nitrite in 27 parts of water is slowly added at at 30 into the solution. As soon as the diazotisation is 30. On completion of the diazotisation, the brown complete, the diazonium compound is filtered off, the dark diazonium monoazo compound is filtered ofi, washed brown filter cake obtained is pasted in 400 parts of water with water and pasted in 400 parts of water. 30.0 parts and coupled with 37.4 parts of the condensation product of the sodium salt of 2-(4'-aminophenylamino) -5-hyfrom 1 mol of cyanuric acid chloride with 2 mols of droxynaphthalene-7-sulphonic acid are dissolved at 80 2-(4'-aminophenylamino) S -hydroxynaphthalene-7-sulin 180 parts of water and the solution is cooled to 40 phonic acid and 1 mol of aniline in 300 parts of water, by the addition of ice. 2.5 parts of sodium acetate are 300 parts of pyridine and parts of sodium carbonate. added and 9 parts of ethylene glycol dichlorocarbonic The next day, the pure blue tetrakisazo dyestufi of the acid ester and 4.9 parts of sodium carbonate in 24 parts formula of water are so added dropwise simultaneously that the OGHsCO OH OH CH: HOQNH-G O- J N=N Nd coon no. NH-Q-NH 0 CHICOOH 0H COOH H018 N \N NHONH-d i l-NEG is precipitated with a little sodium chloride, filtered off, reaction always remains weaklyacid to blue litmus paper. washed free of impurities and dried. It is adark powder After a short time the condensation is complete. 250 which dissolves in water with a pure blue colour and in 40 parts of pyridine and 40 parts of sodium carbonate are concentrated sulphuric acid with a black-green colour. added and the paste of the diazo monoazo dyestufi is Natural or regenerated cellulose fibres are dyed in pure added thereto. The next morning the tetrakisazo dyestuff of the formula OCHrC 0 OH OH HOQNHC OON=N N:

o 0 OH H038 NHC NHCO 2 O CH:

slightly change their shade and have excellent fastness to has precipitated. It is filtered off, washed free from adwashing, acid and light. hering yellow and red impurities and dried. The dark If in this example, the 37.4 parts of the condensation powder so obtained dissolves in water with a pure blue product from 1 mol of cyanuric acid chloride with 2 and in concentrated sulphuric acid with a blue-black mols of 2-(4-aminophenylamino)-5-hydroxynaphthalenecolour. Cellulose dyeings after coppered in the usual 7-sulphonic acid and 1 mol of aniline are replaced by way are a pure greenish blue shade and have excellent 38.0 parts of the condensation product from 1 mol of fa'stness to washing, tartaric acid and light. cyanuric acid chloride with 2 mols of 2-(4-aminophenyl- If instead of the 9.0 parts of ethylene glycol di-chloroamino)-5-hydroxynapthalene-7-sulphonic acid and 1 mol carbonic acid ester, 11.1 parts of diethylene glycol diof p-toluidine, 34.9 parts of the condensation product chlorocarbonic acid ester, 13.2 parts of triethylene glycol from 1 mol of cyanuric acid chloride with 2 mols of di-chlorocarbonic acid ester, 9.7 parts of 1.3-dihydroxy- 2-(4-aminophenylamino) 5 hydroxynaphthalene-7-sulpropane-di-chloroca'rbonic acid ester, 104 parts of 1.2 or phonic acid and 1 mol of ammonia, 34.5 parts of the 1.4-n-dihydroxybutane-di-chlorocarbonic acid ester or the condensationpr-oduct from 1 mol of cyanuric acid chlocorresponding number of parts of the aliphatic dicarride with 2 mols of 2-(4'-arninophenylamino)-5-hydroxyboxylic acid chlorides named in Example 4 are used and naphthalene-7-sulphonic acid and 1 mol of methylarnine, otherwise the same procedure as described in this example 36.4 parts of the condnesation product from 1 mol of is followed, similar dyestuifs with similar properties are cyanuric acid chloride with 2 mols of 2-(4-'aminophenylobtained. amino)-5-hydroxynaphthalene-7-sulphonic acid and 1 mol of diethylamine, 40.0 parts of the condensation product from 1 mol of cyanuric acid chloride with 2 mols of 2-(4'-arninopl1enylamino)' 5 hydroxynaphthalene-7-sulphonic acid and 1 mol of S-amino-2-hydroxybenzene-1- Example 3 27.2 parts of 5-(3-aminobenzoylamino)-2-hydroxybenzene-l-carboxylic acid are diazotised in the usual way with 6.9 parts of sodium nitrite and the diazonium comcarboxylic acid or by 35.6 parts of the condensation pound obtained is coupled with 21.7 parts of l-amino-Z- product from l mol of benzene-1.4- or l.3-dicarboxylic naphthyl glycolic acid in the presence of 20 parts of soacid chloride with Zmols of 2-(4'-aminophenylamino)-5- dium acetate. To accelerate the coupling, 6 parts of amino) 2 hydroxybenzene-l-carboxylic acid, 2856 parts 30.0,- parts oft -(4i-methyl-3 kaminobenzoylamino) -2rhyacid:- The orange-brown suspension of *the'. diazonium sodium carbonate are added dropwise until there is a neutral reacti'om The violet-blue suspensiomof the monoazo dyestuff is mixed with 500 parts of sodium some time, 500 parts of sodium chloride and 100 parts of chloride and 100 parts of concentrated hydrochloric acid concentrated hydrochloric acid are poured inliand the and diazotised by the slow dropwise addition of-.9 parts 5 whole-isdiazotised at 30 with 9 parts of sodium nitrite. of sodium nitrite in 27 parts of water at 30-3'5"; The" Assoon as1-no'- n1or'e aminomonoazo 'dyestuif can. be diazonium compound, after filtering-oflf and washing, is traced,- the diazonium compound is filteredofi; washed pasted in 400 parts of water and coupled-in the presence- 7 with water and pasted in 400 parts of ice-Wa ter. It is of 300 parts of pyridine and 40*parts of sodium carbocoupled with a solution of the condensation product mate with the condensation product obtained by reacting from 530 parts of 2-(4-aminophenylamino)-5-hydroxyparts of 2-(4'-aminophenylamino)-5-hydroxynaphthanaphthalene-7-sulphonic acid and 11.5 parts of sebacic lene-7-sulphonic acid in a neutral aqueous solution'withacidl dichloride in 300 parts of water, 300 parts of pyriphosgene. The tetrakisazo dyestufiof the formula: dine and parts of soda-.- The next day, the precipitated dissolved in 600 parts of water and finally parts of sodium carbonate in 50 parts of water are added. After 0 CHiC O OH OH is filtered ofi theznext day, washedifree =:of byaproducts dyestufi is filtered off, washed, dried' and ground. Th and dried. It is a adark -powder whichdissolves in water tetrakisazo dyestutf so obtained of the formula CHi OCHzCOOH OH with a pure blue and in concentrated sulphuric acid with a .black colour. Natural or regenerated cellulose dyeings whe'n after-copperedhave pure'bluelshades andfarefast is a dark powder and dyesflcellulose fibres when after copperediin pure greenish'blue' shades whichhave excellnt fastness properties. It dissolves in. water with a vto -washing, .acidand light. 'pure blue and in concentrated sulphuric acid with a'blue- If instead o'f'lthe 2.7.2 parts of 5-(.3-aminobenzoylblack colour.

If instead of the condensatiomproduct from 30 parts of of 5 (4'-metliy1 3' aminobenzoylamino)-2lhydroxyben- 2-(4-aminophenylamino) 5 hydroxynaphthalene-7' sulzene-l carboxylic acid, 30.2 parts of. 5"-(4-meth'oxy-3'- phonic. acid and "1115 parts of sebacic acid dichloride, a aminobenzoylamino)-2"- h'ydr'oxybenzene 1 carboxylic condensation product'fromfitlparfs of I2-'(4-aminophenacid, .30Z'65'parts' of "5 (4'-chloro-3' aminobenzoylamino)- ,ylamino)r5-hydroxynaplithalene=7-sulphonicacid and 6.1 2"-liydroxybenzene-l carboxylic acid,-,28.'6" parts of 5I-(3- parts ofoXalic chloride, 7.5 parts of succinic acid dichloaminobenzoylamino)-2 hydroxy-3 or -4-methylbenzeneride, 8.'8pa'rts' of adipic'acid dichloride, 8f2parts of'dil-carboxylic acid, 30.65 .parts! of 5-(3'-aminobenzoylglycolic acid dichloride, .9.t ).parts of thiodiglycolic acid amino)-2-hydroXy-3-chlorobenzene 1 carboxylic acid, dichloride or"7'.4 parts of furnaric acid'dichloride-orone of'th'e condensation products named'in Example 2 is used, then similar dyestuffs with similarly 'good'properties are obtained.

dfioxy-S-methylbenzene-lficarboxylic acid, 35.2.. arts. of 5-(3.-'.-aminobenzoylamino.) -.2 hydroxybenzene .3 sulphonic acid-.l-acarboxylic acid .or 36:6 parts: of-S-(lfmethyl-3'-aminobenzoylamino) 2 hydroxybenzene :3-

'--a x'. 'da use a. rti :comiiffiirfllifii? 1.25;? $22 ilueiiyestifii1153mm Wa e eie fl a l fl m h properties care obtained. usualway with partsof sodiunr n trite" and coupled If=in 'theproduction ofthe above dyestuffs instead of m g fi g EF .parts of the condensationproductfrom: 2.-( 4-aminophenylamii i h 3 i '7' i i acld' F no) 5-hydroxynaphthalene-7 sulphonic acid and phosgene "t gP f ffi- 29F dyszsmfi obtamed 500 parts i such a product'using.thiophosgene-is used, then dyestuffs 2 22 523 0 5 2 ?i izfig igg ig g gia wlthislmllar'pmpemes are also d' 25-30,,are added. The completely formed diazonium compoundisfilteredjoif, washed' withwater and pasted in 400' parts ofwater. It is'then poured into a solution of'the 'condensationproductfrom 60 parts of 2-(4-'-amihydroxy-3-methylbenzene-l-carboxylic acid are dissolved nophenylamino)-5-hydroxynaphthalene-7-sulphonic acid in 400 p arts-.of water and 4 parts of caustic soda lye, and phosgene in 600 parts of water, 400 parts of pyridine 6.9 parts Of sodium nitrite are added and the whole is ,and.4() parts of sodium carbonate, A deep blue solution stirred at 20 in 40 parts-of concentrated hydrochloric is formed immediately. 24 parts of ammonia and the paste ofa dia zomonoazo compound obtained according compound is neutralisedwith 4.8 parts of sodiumwarto Example 2 from 27.2 parts of 5-(4'-a1ninobenzoylbouatee- 20.parts-ofisodium"acetateinu60 parts ofiwater amino)-2-hydroxybenzene-l-carboxylicacid and 21:7 and .-then-.1 2l.7-parts-ofi -1--amino'-2-'naphthyl-glycolic.acid partsofil-amino-Q-naphthylglycolic acid are added; The

Example 5 28.6 parts of 5- (4''-aminobenzoylamino) 3 methy1 2- Example4 30.0 parts of 5-(3-methy1-4'-aminobenzoylamino)-2- 'colour.

in fast green-blue shades.

zene-l-carboxylic acid are diazotised in the known man- 1 next day, the tetrakisazo dyestutf, which has the probable composition:

day the tetrakisazo dyestutf is salted out with sodium chloride, filtered off, washed with diluted sodium chloride OCHaCOOH OH SOsH NEG-III! HOaS l COOH is precipitated with a little sodium chloride, filtered off, washed free of impurities and dried. When ground, it

"is a dark powder which dissolves in water with a pure blue and in concentrated sulphuric acid with a black It dyes cellulose dyeings when after coppered If 27.2 parts of -(4-aminobenzoylamino)-2-hydroxybenzene-l-carboxylic acid or 35.2 parts of 5-(4-aminobenzoylamino)-2-hydroxybenzene-l-carboxylic acid-3-su1- phonic acid are used instead of 28.6 parts of 5-(4'-aminobenzoylamino)- 3 methyl-2-hydroxybenzene-l-carboxylic acid or if instead of the diazomonoazo dyestutf from Example 2, equivalent parts of the diazomonoazo dyestuff from Example 1, 3 or 4 are used to form the tetrakisazo dyestufi and otherwise the same procedure as described in this example is followed, similar dyestufis with similarly good properties are obtained.

Example 6 27.6 parts of 5-(4-aminobenzoylamino)-2 hydroxyben ner and coupled with 25.3 parts of l-amino2-methoxynaphthalenes-G-sulphonic acid in the presence of parts of sodium acetate. The monoazo dyestufi suspension obtained is mixed with volume percent of sodium chloride and 100 parts of concentrated hydrochloric acid and diazotised at 2530 with 9 parts of sodium nitrite. After stirring overnight, the diazomonoazo dyestuii is filtered off, washed with water and pasted in 400 parts of water. It is coupled with 40.0 parts of the condensation product from one mol of cyanuric acid chloride, 2 mols of 2-(4'-aminophenylamino) -5-hydroxynaphthalene-7-su1phonic acid and pyridine and 20 parts of sodium bicarbonate. The next NH-C O-N=N N= dornooon H solution, dried and ground. The tetrakisazo'dyestufi of the formula:

*OCHI on HOQNH-O ON==N N==N 00 on no. NH-O-NH 1 N .H NEi aNH dissolves in water with a pure blue and in concentrated sulphuric acid with a green-black colour. The aftercoppered dyeings on cellulose fibers are distinguished by their pure blue shade and by good fastness to wet.

If in this example, instead of the 25.3 parts of l-amino- 2-methoxynaphthalene-6-sulphonic acid, the same amounts of 1-amino-2-methoxynaphthalene 7 sulphonic acid or 26.7 parts of 1-amino-2-ethoxynaphthalene-6- or -7-sulphonic acid are used to form the tetrakisazo dyestufl, then similar blue dyestuffs are obtained.

Example 7 1.0 part of the dyestutf obtained according to Example 2 and 2 parts of soda are dissolved in a dyebath containing 3000 parts of water. 100 parts of cotton are entered at 4050, the bath is heated to 90-95 within 30 minutes, 30 parts of sodium sulphate are added and dyeing is continued for 45 minutes at this temperature. After this time, the dyebath is completely exhausted. The dyed goods are rinsed cold and after-treated at in a fresh bath containing 2 parts of crystallised copper sulphate in '2000 parts of water and 2 parts of 30% acetic acid. The goods are rinsed and dried in the usual way. The cotton is dyed in pure greenish-blue shades which have good washing, water, perspiration and light fastness properties.

What I claim is:

1. A tetrakisazo dyestuti having the general formula:

v on

H-O-NH-B-NHONH .sodI

wherein B is a bivalent radical selected from-the group consisting of carbonyl, biscarbonyl-alkylene, biscarbonylphenylene, bis-(carbonyloxy) -alkylene and 1,3,5-triaziny1 radicals, A and A.'. represent radicals of the tormulaz Y H000 N=N HO NH 06 wherein X represents a member selected :fromtth'egroup consisting of hydrogen, chlorine, the ;methy1tamd the s ulphonic acid group,

Y represents a member selected from the group consisting 15 of hydrogen, chlorine, the methyl and the methoxy group,

one Z represents hydrogen and the other Z represents a member selected from the group consisting of hydrogen and the sulphonic acid group, 20

R represents a member selected from the group consisting of methyl, ethyl and carboxymethyl radicals.

2. A tetrakisazo dyestuflt' having the general formula:

if) wherein ;Bl;isr.a:1 bivalentrradicallselctezhfromzther group -.consisting of carbonyl, biscarbonyl-alkylene, biscarbonylphenylene, bis-(carbonyloxy)-alkylene and 1,3,,5-triazinyf1 radicals, Aand.Airepresentradicalspfi'the formulazl wherein OH on A A! Hots NH-O-NH-B-NH-O-NH sotn OOH 3. A tetrakisazo dyestufl having the formula:

OOHQCOOH OH =N H018 NEG-NH OCHrCOOH OH I o HoQNH-oo N= -N=N- I? 0 OH Hols NH-O-NH- c-NHQ SOzH 4. A tetrakisazo dyestufi having the formula:

OCHzCO OH OH -OCH:

5. A tetrakisazo dyestufi having the formula:

0H 0 CHaC O OH =C O NH HOaS- 2 6. A tetrakisazo dyestufi having the formula:

(CHIN NHQ-NH-o o- '7. A tetrakisazo dyestufi having the formula:

0 CHaCOOH 0H References Cited in the file of this patent UNITED STATES PATENTS Delfs et a1 Aug. 2, 1938 Anderau Ian. 6, 1942 Kaiser Dec. 18, 1945 Grandiean Ian. 11, 1949 OOH: 

1. A TETRAKISAZO DYESTUFF HAVING THE GENERAL FORMULA: 